Copolymers of oxidized isobutylene fractions with hydrocarbons



tion of elastomeric resins. However, inclusion of fractions 1 and 4 orboth before or after the reaction in the presence of copolymerizingcatalyst aflfords an additiona1 means of varying the nature 1 of thefinished product. 7

The nature of the present invention and type of results obtained areillustrated further by the following examples although these data shouldnot be misconstrued to limit unduly the broad scope of the invention. 7

Example I aromatic hydrocarbon at a temperature from about -50 to about+20 C. in the presence of a Friedel-Crafts catalyst, said oxidationproducts resulting from the reaction of isobutylene with oxygen at atemperatureoi from-about 180 C. to 300 C. and at a pressuregreaterthan:about 35 atmospheres.

- 3. A process for producing a resin which comprises reacting a fractionof isobutylene oxidation products boilingabove about 140 C. with atleast one member of the group consisting of a conjugated diolefin and avinyl aromatic hydrocarbon in the presence of a Friedel-Crafts catalystat a temperature offrom about 50 to about +20 introduced into aspherical reaction zone of 70 cc.

capacity at flow rates of 3 and 15 mols. per hour, respectively.Apressure of 1200 p. s. i. and temperature'of220" C. were maintained inthe reactor. Reaction. was initiated by a glow coil and.

was self-sustaining thereafter. Liquid products, after removel ofunreacted isobutylene, was produced at a rate of 260 grams per hour.

The product was vacuum distilled to give an.

essentially non-volatile fractionvboiling above 140 C. which comprisedessentially fractions 2,

3 and 40f the fractions cited above. This nonvolatile". fraction wasmixed with an approximately equal volume of styrene. at -10 C.Additionof a BF3(C2H5)2O catalyst resulted in an exothermic reaction.The product was extracted with alcohol and approximately 70% by weightof alsoft, rubber-like material exhibiting elastomeric properties wasobtained.

' Example 11* The non-volatile fraction of partially oxidizedisobutylene boiling above 140 C. was mixedwith an approximately equalvolume 'of butadiene at -10 C. Approximately 11 1%. .by volume ofBFa(CzH)2O.- as catalyst: was addedwdropwise resulting in an exothermicreaction. The product- .was extracted with alcohol, and. approximately65% by weight of the charged materials was recovered as a rubber-likematerial.

Example III 1 The non-volatile, fraction of partially oxidizedisobutylene boiling above 140 .C. was mixed with approximately an equalvolume of a 50-50 mixe ture of styrene and butadiene at C. Approximately1% catalyst was added dropwise, resulting in an exothermic reaction. Theproduct was extracted with alcohol, and approximately 80% by weight ofthe charged materials were recoveredas a soft, rubber-like materialexhibiting elastomeric properties. H

We claim as our invention: 1., A process for producing a resin whichcomprises reacting a fraction of isobutylene oxidation products boilingabove about 140 C. with 3/0011.

jugated diolefin at a temperature from about.

.50 .to about C. in the presence of a Friedel-Crafts catalyst, saidoxidation products resulting. from the reaction of isobutylene withoxygen at atemperature of from about 180 C.:to 300 Crandat apressuregreater than about 35 atmospheres.-; 1 Y

2. A process for producing a resin which com prises reacting afractionof isobutylene oxidation products boiling above about 140 C. with avinyl by. volume .of ,BF3(C2H5)20 as,

C., said oxidation products resulting from the reaction of isobutylenewith oxygen at a temperature-bf'from about 180 C. to 300 C. and at apressure greater than about 35 atmospheres.

4. Aprocess for producing a resin which comprises reacting a fraction ofisobutylene oxidation products boiling above about .C. with at least onemember of the: group consisting of a conjugated diolefin and a vinylaromatic hydrocarbon in thepresence-of a boron trifiuoride catalyst at atemperature of from about 50 to about +20 0., said oxidation productsresulting from the reaction of isobutylene with oxygen at a temperatureof from about C. to .30,0,C.-and at a pressure greaterthanabout-3.5.atmospheres. v

5. A processior producing a resin which comprises reacting a fraction ofisobutylene oxidation products boiling above about 140 C. with at leastone member jof the group. consisting of a conjugated diolefin and avinyl aromatic hydrocarbon1 in thepresent otla boron trifluoride-ethercatalyst at a temperature of from about '-50 to about +20 C., saidoxidation products resulting from thereaction of isobutylene with oxygenat a tem-.

of a boron trifiuoride-ether catalyst at a temperatureof from about 50to about +20,C., said oxidation products resulting from .the reaction ofisobutylene with oxygen ata temperature of from about 180 C. to 300 C.and at a pressure greater than about 35 atmospheres. p

7. A process for producingca resin which comprises reacting a fractionof isobutylene oxidationproducts boiling aboveabout 140 C.xwith buta-(fiche-1,3 in the presence of .a borontrifluorideether catalyst atxa,temperature .of from about 50 to about +20".C.;:said:oxidationzproductsresulting-from the reaction of isobutylene with oxygen at a temperatureof from about 180 C. to 300C. and at a pressuregreater'than about 35atmospheres. Y J

8. A process for. producing a resin which comprises reacting a fractionof isobutylene oxidation products boiling above about 140 C. withstyrene in the presence of a boron trifiuoride-ether catalyst at atemperature of from about 50 to about +20 C., saidoxidationproductsresulting from the reaction of isobutylene with oxygenat a-temperature of from about180 C.- to 300, C..and at a' pressuregreater than about 35 atmospheres.

. 9. .A'processfor. producing awresin which comprisesreacting at atemperature from aboutr-50 to about+20-C.-in the-presence .of a Friedel-Crafts catalyst a conjugated diolefin. and avinyl aromatic' hydrocarbon.with. a fraction .of. liquids boiling above about H090. and resultingfrom the.

reaction of isobutylene with oxygen at a temperature of from about 180to about 300 C. and at a pressure greater than about 35 atmospheres.

10. A process for producing a resin which comprises reacting at atemperature from about -50 to about +20 C. in the presence of a Friedel-Crafts catalyst at least one member of the group consisting of aconjugated diolefin and a vinyl aromatic hydrocarbon with a fraction ofliquids boiling above about 140 C. and resulting from the reaction of analiphatic monoolefinic hydrocarbon of not more than five carbon atomswith oxygen at a temperature of from about 180 to about 300 C. and at apressure greater than about 35 atmospheres.

11. A resin comprising the copolymer of at least one member of the groupconsisting of a conjugated diolefin and. a vinyl aromatic hydrocarbonwith a fraction of liquids boiling above about 140 C. and resulting fromthe reaction of isobutylene with oxygen at a temperature of from about180 to about 300 C. and at a pressure greater than about 35 atmospheres.

12. A resin comprising the copolymer of at least one member of the groupconsisting of a conjugated diolefin and a vinyl aromatic hydrocariconwith a fraction of liquids boiling above about 140 C. and resulting fromthe reaction of an aliphatic monoolefinic hydrocarbon of not more thanfive carbon atoms with oxygen at a temperature of from about 180 toabout 300 C. and at a pressure greater than about 35 atmospheres.

13. A resin comprising the copolymer of a conjugated diolefin and afraction of liquids boiling I 6 above about 140 C. and resulting fromthe reaction of isobutylene with oxygen at a temperature of from about180 to about 300 C. and at a pressure greater than about atmospheres.

14. A resin comprising the copolymer of a vinyl aromatic hydrocarbon anda fraction of liquids boiling above about C. and resulting from thereaction of isobutylene with oxygen at a temperature of from about toabout 300 C. and at a pressure greater than about 35 atmospheres.

15. A resin comprising the copolymer of a conjugated diolefin, a vinylaromatic hydrocarbon. and a fraction of liquids boiling above about 140C. and resulting from the reaction of isobutylene with oxygen at atemperature of from about 180 to about 300 C. and at a pressure greaterthan about 35 atmospheres.

EDWARD M. GEISER. ARMAND J. 1m RossE'r.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,212,900 Groll Aug. 27, 19402,438,340 Johnson Mar. 23, 1948 FOREIGN PATENTS Number Country Date360,822 Great Britain Oct. 30, 1 931 667,163 Germany Nov. 5, 1938

12. A RESIN COMPRISING THE COPOLYMER OF AT LEAST ONE MEMBER OF THE GROUPCONSISTING OF A CONJUGATED DIOLEFIN AND A VINYL AROMATIC HYDROCARBONWITH A FRACTION OF LIQUIDS BOILING ABOVE ABOUT 140* C. AND RESULTINGFROM THE REACTION OF AN ALIPHATIC MONOLEFINIC HYDROCARBON OF NOT MORETHAN FIVE CARBON ATOMS WITH OXYGEN AT A TEMPERATURE OF FROM ABOUT 180*TO ABOUT 300* C. AND AT A PRESSURE GREATER THAN ABOUT 35 ATMOSPHERES.